CN111672539B - 一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法 - Google Patents
一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法 Download PDFInfo
- Publication number
- CN111672539B CN111672539B CN202010543965.0A CN202010543965A CN111672539B CN 111672539 B CN111672539 B CN 111672539B CN 202010543965 A CN202010543965 A CN 202010543965A CN 111672539 B CN111672539 B CN 111672539B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- oxygen cluster
- tungsten
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 35
- 230000023556 desulfurization Effects 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 19
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 13
- -1 nickel-substituted tungsten oxygen Chemical class 0.000 claims abstract description 17
- 239000007983 Tris buffer Substances 0.000 claims abstract description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- SRJOCJYGOFTFLH-UHFFFAOYSA-N isonipecotic acid Chemical compound OC(=O)C1CCNCC1 SRJOCJYGOFTFLH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 abstract description 3
- LBUSGXDHOHEPQQ-UHFFFAOYSA-N propane-1,1,1-triol Chemical compound CCC(O)(O)O LBUSGXDHOHEPQQ-UHFFFAOYSA-N 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 14
- 238000010586 diagram Methods 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000240 adjuvant effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001907 polarising light microscopy Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- RAFNAMHEPCFDRC-UHFFFAOYSA-N [W].[Mo].[Co].[Ni] Chemical compound [W].[Mo].[Co].[Ni] RAFNAMHEPCFDRC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical group [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域
本发明涉及催化剂制备技术领域,具体涉及一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法。
背景技术
近年来,雾霾天气频频出现,此环境问题已严重困扰我国。雾霾的主要监控指标是PM2.5,严重的雾霾天气不仅会对交通和出行造成重大影响,而且也会对人体造成相当巨大的损伤。随着经济的迅速发展,富裕起来的人越来越多,汽车保有量也快速增长,随之带来的大量尾气排放。研究表明,这已经成为雾霾的主因之一。相比于带来雾霾,汽车尾气中还有一项更为重要的环境质量指标就是SO2的含量,会带来更大的环境伤害。因此,世界各国很早就意识到汽车油品中硫含量的重要性,并且制定了相关法律法规进行严格控制。因而炼油业面临巨大的挑战,如何在汽车燃料需求的不断增加而环保法规日益严格的双重压力下,炼制更高标准的车用汽柴油就成为了一个重大的技术难题,其中最为核心的技术之一就是利用新技术如何更加便宜和高效的进行脱硫,以使油品的硫含量达到甚至超过国V标准。当前,工业上汽柴油脱硫最为流行的脱硫方法是使用加氢催化剂进行加氢催化脱硫,这是一个费效比最低的办法。目前,大部分的加氢脱硫催化剂主要采用两种制备方法:直接硫化态法或氧化态硫化法。前者主要采用热解适宜的金属硫化物。另外一种方法是将含有氧化态金属组分的浸渍液负载于载体上,焙烧,硫化,而氧化铝负载的含有助剂Ni(Co)的MoS2催化剂是当前最常用的一种。然而,这些方法也存在一些较大的缺点,如所采用的金属硫化物毒性较大;且其制备复杂,生过程中会产生大量有毒物质,严重污染环境等,这些缺点也限制了其大规模工业应用。
多酸,也被称为多金属氧酸盐(Polyoxometalates,缩写为POMs),是骨架结构中由Mo、W、V、Nb和Ta等前过渡元素构筑的一类金属-氧簇(Metal-Oxo Clusters)化合物。由于多酸表现出来的各种优异性质,例如荧光、催化活性、以及单分子磁体等,POMs已经引起了人们的极大关注。多酸类化合物具有制备简单、组成明确、结构稳定、低毒环保等特点,在环境科学、医学诊断以及药物化学等方面有潜在的应用前景。
发明内容
由于助剂原子与硫化有效成分钼(钨)原子的比例即镍/钨的提高,有利于催化活性的提高,故多核镍取代的钼(钨)多酸具有很大的催化优势。故本发明以镍(钴)钼(钨)双金属多酸簇为加氢脱硫催化剂前驱体,通过研究催化剂的构效关系,调控活性结构,了一种新型高效、绿色环保的多酸类加氢催化脱硫催化剂。
本发明是通过以下技术方案实现的:
一种六核镍取代钨氧簇加氢催化脱硫催化剂,所述催化剂的分子式为:{[Ni6(OH)(en)2(TRIS)(H2O)2(L)2(PW9O34)]·2H2O,其中en为乙二胺,TRIS为三羟甲基乙烷二价负离子,L为4-哌啶甲酸两性离子,化学式为C20H59N6PNi6O47W9,所述催化剂属于正交晶系,空间群为Pnma,化合物晶胞参数为: α=β=γ=90°,Z=4,所述催化剂的结构为:结构中有一通过共边连接所形成的呈1-2-3排列的等边近似平面的六核镍-氧簇块,该六核镍-氧簇块被两分子乙二胺和一分子TRIS及2个4-哌啶甲酸两性离子共同修饰,所述六核镍-氧簇带9个电荷,被三缺位的钨-氧簇块围成一圈的近似共面的六个钨上的氧及一个磷四面体上的氧螯合。
本发明还提供一种六核镍取代钨氧簇加氢催化脱硫催化剂的制备方法,按重量份计,将2-4份三缺位前驱体Na9PW9O34·nH2O、0.8-1.2份4-哌啶甲酸、0.8-1.2份三羟甲基乙烷和7-9份NiCl2·6H2O依次加入到8-12份醋酸钠-醋酸缓冲溶液中,搅拌4-6分钟后,用移液管逐滴加入2-4份乙二胺,继续搅拌50-70min后,装入带有聚四氟乙烯内衬的不锈钢反应釜中,密封并置于165-175℃的烘箱中加热70-75小时,取出后自然冷却至室温,得到绿色柱状晶体为六核镍取代钨氧簇加氢催化脱硫催化剂。
具体地,所述醋酸钠-醋酸缓冲溶液的摩尔浓度为0.5mol/L,pH值为4.8。
本发明还提供一种六核镍取代钨氧簇加氢催化脱硫催化剂的使用方法,所述催化剂在使用时固载在γ-Al2O3上,制得催化剂{Ni6PW9}/γ-Al2O3,具体操作方法为:用催化剂配制质量浓度为15-20%的浸渍液,然后采用等体积浸渍法浸渍于γ-Al2O3上,然后放入110-130℃烘箱内干燥1.5-2.5h,再将样品放入管式炉中升温至290-310℃在N2气氛中焙烧3.5-4.5h,得到催化剂{Ni6PW9}/γ-Al2O3。
由以上的技术方案可知,本发明的有益效果是:
1)本发明提供的催化剂,结构具有可设计性、可调控性和可确定性,不仅同时含有助剂原子镍和硫化有效成分钼原子和钨原子,且具有更高的镍钨比(达到0.667),并可进选择多种有机基团进行共价有机官能化,提高其分散性,进而提高其催化性能;更为重要的是,本发明提供的催化剂可通过X-射线来明确其组成和分子结构,并且因为是镍取代型,故镍原子能与钨原子通过氧桥紧密相连,有助于提高催化剂的催化脱硫活性;
2)本发明提供的催化剂比工业上的镍钼加氢催化脱硫催化剂具有更高的热稳定性,可以进行深化脱硫。
附图说明
图1为L的结构示意图;
图2为TRIS的结构示意图;
图3为六核镍取代钨氧簇加氢催化脱硫催化剂中的六核镍簇单元结构多面体示意图;
图4为催化剂的单晶结构多面体示意图;
图5为六核镍取代钨氧簇加氢催化脱硫催化剂的红外图;
图6为六核镍取代钨氧簇加氢催化脱硫催化剂理论模拟、实验测得的粉末衍射图;
图7为六核镍取代钨氧簇加氢催化脱硫催化剂的热重分析图;
图8为预硫化后的催化剂{Ni6PW9}/γ-Al2O3的粉末衍射图;
图9为催化剂{Ni6PW9}/Al2O3、参比催化剂NiW和载体γ-Al2O3的孔径分布图;
图10为催化剂{Ni6PW9}/Al2O3、参比催化剂NiW的探针分子的原位红外光谱图(DRIFT);
图11为硫化态催化剂的高分辨率透射电镜照片;
图12为二苯并噻吩(DBT)在镍钼催化剂上的加氢催化脱硫反应网络图。
图13为在工作条件下,在120分钟时,催化剂{Ni6PW9}/Al2O3和参比催化剂NiW对DBT的转化率。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
一种六核镍取代钨氧簇加氢催化脱硫催化剂,所述催化剂的分子式为:{[Ni6(OH)(en)2(TRIS)(H2O)2(L)2(PW9O34)]·2H2O,其中en为乙二胺,TRIS为三羟甲基乙烷二价负离子,L为4-哌啶甲酸两性离子,化学式为C20H59N6PNi6O47W9,所述催化剂属于正交晶系,空间群为Pnma,化合物晶胞参数为: α=β=γ=90°,Z=4,所述催化剂的结构为:结构中有一通过共边连接所形成的呈1-2-3排列的等边近似平面的六核镍-氧簇块,该六核镍-氧簇块被两分子乙二胺和一分子TRIS及2个4-哌啶甲酸两性离子共同修饰,所述六核镍-氧簇带9个电荷,被三缺位的钨-氧簇块围成一圈的近似共面的六个钨上的氧及一个磷四面体上的氧螯合。
本发明还提供一种六核镍取代钨氧簇加氢催化脱硫催化剂的制备方法,按重量份计,将0.3克三缺位前驱体Na9PW9O34·nH2O、0.1克4-哌啶甲酸、0.1克三羟甲基乙烷和0.8克NiCl2·6H2O依次加入到10克醋酸钠-醋酸缓冲溶液中,搅拌5分钟后,用移液管逐滴加入0.3克乙二胺,继续搅拌60min后,装入带有聚四氟乙烯内衬的不锈钢反应釜中,密封并置于170℃的烘箱中加热72小时,取出后自然冷却至室温,得到绿色柱状晶体为六核镍取代钨氧簇加氢催化脱硫催化剂。
具体地,所述醋酸钠-醋酸缓冲溶液的摩尔浓度为0.5mol/L,pH值为4.8。
本发明还提供一种六核镍取代钨氧簇加氢催化脱硫催化剂的使用方法,所述催化剂在使用时固载在γ-Al2O3上,制得催化剂{Ni6PW9}/γ-Al2O3,具体操作方法为:用催化剂配制质量浓度为18%的浸渍液,然后采用等体积浸渍法浸渍于γ-Al2O3上,然后放入120℃烘箱内干燥2h,再将样品放入管式炉中升温至300℃在N2气氛中焙烧4h,得到催化剂{Ni6PW9}/γ-Al2O3。
催化剂的加氢催化脱硫活性评价:
二苯并噻吩(DBT)是油品中最难脱除的含硫化合物之一,经常被用作模型化合物评价催化剂的加氢催化脱硫活性。DBT加氢催化脱硫主要有两条平行的路径,如图13所示。一条为直接氢解,即C-S首先断裂生成联苯(BP)。另一条为加氢途径,即C-S不断裂,而先进行加氢。在镍钨催化剂上反应的主要产物为BP、CHB及其异构体。将1g催化剂和60mLDBT的十氢萘溶液(硫含量为850μg/)先后加入到100mL高压釜中。高压釜内反应温度为300℃,通入H2,总压为8Mpa,连续搅拌4h。实验为了避免内外扩散对反应造成影响,选择催化剂的粒径为0.25mm,反应器搅拌速度设定为1000rpm,这样的条件可忽略内外扩散对反应的限制作用。
如图1-图4所示,其中图1为L的结构示意图,图2为TRIS的结构示意图,图3为六核镍取代钨氧簇加氢催化脱硫催化剂中的六核镍簇单元结构多面体示意图,其中白色八面体为镍-氧八面体;图4为催化剂的单晶结构多面体示意图,图片最下方黑色八面体为钨-氧八面体,上方白色八面体为镍-氧八面体,中间处四面体为磷-氧四面体,为了简洁,结晶水分子省略。图5为六核镍取代钨氧簇加氢催化脱硫催化剂的红外图;图6为六核镍取代钨氧簇加氢催化脱硫催化剂理论模拟、实验测得的粉末衍射图;图7为六核镍取代钨氧簇加氢催化脱硫催化剂的热重分析图;图8为预硫化后的催化剂{Ni6PW9}/γ-Al2O3的粉末衍射图,在相应的位置没有出现WO3的衍射峰,这表明在催化剂制备过程中,其表面钨组分分散性较好,钨组分以无定型或者尺寸小于4nm的晶粒存在。图9为催化剂{Ni6PW9}/Al2O3、参比催化剂NiW和载体γ-Al2O3的孔径分布图,属于典型的IV型曲线,表明它们的孔结构以介孔为主。图10为催化剂{Ni6PW9}/Al2O3、参比催化剂NiW的探针分子的原位红外光谱图(DRIFT),2088cm-1周围出现的吸收峰是没有助剂作用的WS2相的CO伸缩振动峰;而2064cm-1周围出现的吸收峰是有助剂作用的WS2相(Ni-W-S活性位)的CO伸缩振动峰,含有镍助剂的Ni-W-S活性位更容易被氧化,结果表明催化剂{Ni6PW9}/Al2O3比参比催化剂NiW表面含有更多的Ni-Mo-S活性位,催化活性更高。图11为硫化态催化剂的高分辨率透射电镜照片,其中a对应于催化剂{Ni6PW9}/Al2O3,b对应于参比催化剂NiW,图中的每一条黑色条纹代表一层WoS2晶簇,平行黑色条纹的间距大约为0.64nm,WS2晶簇的形态和分散度是影响硫化态催化剂活性的重要因素,总体来说,这些硫化后的催化剂表面的WS2晶簇堆垛层数为2-3层,长度为2-4nm,它们在催化剂表面的分散性较好。图13为在工作条件下,在120分钟时,催化剂{Ni6PW9}/Al2O3对DBT的转化率可达97.2%,而参比催化剂NiW在同等条件下仅为63.8%,展现出本实施例中的目标催化剂较参比催化剂高得多的转化率。
以上所描述的实施例是本发明一部分实施例,而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围,而是仅仅表示本发明的选定实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
Claims (3)
1.一种六核镍取代钨氧簇加氢催化脱硫催化剂的制备方法,其特征在于,所述六核镍取代钨氧簇加氢催化脱硫催化剂的分子式为:[Ni6(OH)(en)2(TRIS)(H2O)2(L)2(PW9O34)]·2H2O,其中en为乙二胺,TRIS为三羟甲基乙烷二价负离子,L为4-哌啶甲酸两性离子,化学式为C20H59N6PNi6O47W9,所述催化剂属于正交晶系,空间群为Pnma,化合物晶胞参数为:α=β=γ=90°,Z=4,所述催化剂的结构为:结构中有一通过共边连接所形成的呈1-2-3排列的等边近似平面的六核镍-氧簇块,该六核镍-氧簇块被两分子乙二胺和一分子TRIS及2个4-哌啶甲酸两性离子共同修饰,所述六核镍-氧簇带9个电荷,被三缺位的钨-氧簇块围成一圈的近似共面的六个钨上的氧及一个磷四面体上的氧螯合;
六核镍取代钨氧簇加氢催化脱硫催化剂的制备方法,包括以下步骤:按重量份计,将2-4份三缺位前驱体Na9PW9O34·nH2O、0.8-1.2份4-哌啶甲酸、0.8-1.2份三羟甲基乙烷和7-9份NiCl2·6H2O依次加入到8-12份醋酸钠-醋酸缓冲溶液中,搅拌4-6分钟后,用移液管逐滴加入2-4份乙二胺,继续搅拌50-70min后,装入带有聚四氟乙烯内衬的不锈钢反应釜中,密封并置于165-175℃的烘箱中加热70-75小时,取出后自然冷却至室温,得到绿色柱状晶体为六核镍取代钨氧簇加氢催化脱硫催化剂。
2.根据权利要求1所述的一种六核镍取代钨氧簇加氢催化脱硫催化剂的制备方法,其特征在于,所述醋酸钠-醋酸缓冲溶液的摩尔浓度为0.5mol/L,pH值为4.8。
3.一种六核镍取代钨氧簇加氢催化脱硫催化剂的使用方法,其特征在于,所述六核镍取代钨氧簇加氢催化脱硫催化剂采用权利要求1-2中任一项所述的制备方法进行制备得到的;所述六核镍取代钨氧簇加氢催化脱硫催化剂在使用时固载在γ-Al2O3上,制得催化剂{Ni6PW9}/γ-Al2O3,具体操作方法为:用六核镍取代钨氧簇加氢催化脱硫催化剂配制质量浓度为15-20%的浸渍液,然后采用等体积浸渍法浸渍于γ-Al2O3上,然后放入110-130℃烘箱内干燥1.5-2.5h,再将样品放入管式炉中升温至290-310℃在N2气氛中焙烧3.5-4.5h,得到催化剂{Ni6PW9}/γ-Al2O3。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010543965.0A CN111672539B (zh) | 2020-06-15 | 2020-06-15 | 一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010543965.0A CN111672539B (zh) | 2020-06-15 | 2020-06-15 | 一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111672539A CN111672539A (zh) | 2020-09-18 |
CN111672539B true CN111672539B (zh) | 2023-02-28 |
Family
ID=72436111
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010543965.0A Active CN111672539B (zh) | 2020-06-15 | 2020-06-15 | 一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111672539B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112934262B (zh) * | 2021-02-01 | 2021-10-26 | 北京理工大学 | 一种镍取代钨氧簇有机骨架材料及其制备方法和用途 |
CN114275818B (zh) * | 2021-12-29 | 2023-04-11 | 宁德师范学院 | 一种含铜Weakley型钨氧簇化合物、制备方法及其抗肿瘤应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102218348A (zh) * | 2011-04-27 | 2011-10-19 | 哈尔滨师范大学 | 取代型钼磷酸盐晶体催化剂的制备方法 |
WO2012085357A1 (fr) * | 2010-12-22 | 2012-06-28 | IFP Energies Nouvelles | Procede d'hydrodesulfuration de coupes essences utilisant un catalyseur a base d'heteropolyanions pieges dans un support silicique mesostructure |
CN103111335A (zh) * | 2013-01-11 | 2013-05-22 | 长春理工大学 | 基于Dawson型多钨酸盐的离子晶体型可见光催化剂及其制备方法 |
CN106693997A (zh) * | 2017-01-10 | 2017-05-24 | 中国石油大学(华东) | 一种柴油加氢脱硫催化剂及其制备方法和应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3004968B1 (fr) * | 2013-04-30 | 2016-02-05 | IFP Energies Nouvelles | Procede de preparation d'un catalyseur a base de tungstene utilisable en hydrotraitement ou en hydrocraquage |
-
2020
- 2020-06-15 CN CN202010543965.0A patent/CN111672539B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012085357A1 (fr) * | 2010-12-22 | 2012-06-28 | IFP Energies Nouvelles | Procede d'hydrodesulfuration de coupes essences utilisant un catalyseur a base d'heteropolyanions pieges dans un support silicique mesostructure |
CN102218348A (zh) * | 2011-04-27 | 2011-10-19 | 哈尔滨师范大学 | 取代型钼磷酸盐晶体催化剂的制备方法 |
CN103111335A (zh) * | 2013-01-11 | 2013-05-22 | 长春理工大学 | 基于Dawson型多钨酸盐的离子晶体型可见光催化剂及其制备方法 |
CN106693997A (zh) * | 2017-01-10 | 2017-05-24 | 中国石油大学(华东) | 一种柴油加氢脱硫催化剂及其制备方法和应用 |
Non-Patent Citations (3)
Title |
---|
Amino Acid Functionalization of {Ni6PW9}-Based Clusters Under Hydrothermal Conditions;Bin Cai 等;《J Clust Sci》;20141231;第1283–1293页 * |
基于杂多酸簇为前驱体的加氢脱硫催化剂研究进展;梁吉雷等;《精细石油化工》;20170918(第05期);第75-81页 * |
水热合成六核铜簇取代缺位多金属氧酸盐的晶体结构及表征;薛韩等;《黑龙江科学》;20170223(第04期);第116-18页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111672539A (zh) | 2020-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4156859B2 (ja) | 軽油の水素化処理触媒及びその製造方法並びに軽油の水素化処理方法 | |
CN111672539B (zh) | 一种六核镍取代钨氧簇加氢催化脱硫催化剂及其制备方法和使用方法 | |
JP4472556B2 (ja) | 炭化水素油の水素化処理触媒及びその製造方法並びに炭化水素油の水素化処理方法 | |
CN101550044B (zh) | 多金属氧簇/二氧化硅催化剂在硫化物可控氧化中的应用 | |
CN103182310B (zh) | 一种馏分油加氢处理催化剂制备方法 | |
RU2534998C1 (ru) | Катализатор гидроочистки углеводородного сырья | |
CN104069884B (zh) | 一种重油加氢催化剂及其制备方法 | |
CN101491765A (zh) | 一种硫化型加氢催化剂的制备方法 | |
JPWO2004054712A1 (ja) | 軽油の水素化処理触媒及びその製造方法並びに軽油の水素化処理方法 | |
RU2534997C1 (ru) | Способ приготовления катализатора гидроочистки углеводородного сырья | |
WO2011103698A1 (zh) | 加氢精制催化剂 | |
JP4864106B2 (ja) | 炭化水素油の水素化処理触媒の製造方法 | |
Zhu et al. | Ni-BTC metal-organic framework loaded on MCM-41 to promote hydrodeoxygenation and hydrocracking in jet biofuel production | |
CN106927476B (zh) | Mo-SBA-15分子筛及加氢催化剂的制备方法 | |
CN108465484A (zh) | 一种fcc汽油脱硫加氢改质催化剂的制备方法 | |
CN103143365B (zh) | 一种加氢催化剂及其制备方法 | |
CN101153228A (zh) | 用于柴油加氢脱硫的多金属本体催化剂及制法和应用 | |
CN104437578A (zh) | 一种加氢脱硫催化剂、制备方法及其应用 | |
CN108236965A (zh) | 一种改性的加氢脱硫催化剂及其制备方法 | |
CN108568309A (zh) | 一种油品深度加氢脱硫催化剂及其制备方法 | |
CN111921561A (zh) | 一种分级中空结构NH2-MIL-125(Ti)脱硫催化剂的制备方法 | |
CN114917935B (zh) | 一种H2分子原位调控Ni-MoS2加氢脱硫催化剂制备方法及应用 | |
CN101058074A (zh) | 一种重质馏份油加氢处理催化剂 | |
CN115770591A (zh) | 过渡金属掺杂二硫化钼/碳复合材料及其制备方法和应用 | |
CN102319567A (zh) | 一种埃洛石负载钴基催化剂的制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |